Chemical noise produced by equilibrium adsorption/desorption of surface pyridine at Au-Ag-Au bimetallic atom-scale junctions studied by fluctuation spectroscopy.

The chemical noise contained in conductance fluctuations resulting from adsorption and desorption of pyridine at Au-Ag-Au bimetallic atom-scale junctions (ASJs) exhibiting ballistic electron transport is studied using fluctuation spectroscopy. ASJs are fabricated by electrochemical Ag deposition in a Au nanogap to produce a high-conductance Ag quantum wire, followed by electromigration-induced thinning in pyridine solution to create stable ASJs. The conductance behavior of the resulting ASJs is analyzed by sequential autocorrelation and Fourier transform of the current-time data to yield the power spectral density (PSD). In these experiments the PSDs from Ag ASJs in pyridine exhibit two main frequency regions: 1/f noise originating from resistance fluctuations of the junction itself at low frequencies, and a Lorentzian noise component arising from molecular adsorption/desorption fluctuations at higher frequencies. The characteristic cutoff frequency of the Lorentzian noise component determines the relaxation time of molecular fluctuations, which, in turn, is sensitive to the kinetics of the adsorption/desorption process. The kinetics are found to depend on concentration and on the adsorption binding energy. The junction size (<5G0), on the other hand, does not affect the kinetics, as the cutoff frequency remains unchanged. Concentration-dependent adsorption free energies are interpreted as arising from a distribution of binding energies, N(E(b)), on the Ag ASJ. Other observations, such as long lifetime ASJs and two-level fluctuations in conductance, provide additional evidence for the integral role of the adsorbate in determining ASJ reorganization dynamics.

Convective delivery of electroactive species to annular nanoband electrodes embedded in nanocapillary-array membranes.

Significant technological drivers motivate interest in the use of reaction sites embedded within nanometer-scale channels, and an important class of these structures is realized by an embedded annular nanoband electrode (EANE) in a cylindrical nanochannel. In this structure, the convective delivery of electroactive species to the nanoelectrode is tightly coupled to the electrochemical overpotential via electroosmotic flow. Simulation results indicate that EANE arrays significantly outperform comparable microband electrode/microchannel structures, producing higher conversion efficiencies at low Peclet number. The results of this in-depth analysis are useful in assessing possible implementation of the EANE geometry for a wide range of electrochemical targets within microscale total analysis systems.

Enhanced mass transport of electroactive species to annular nanoband electrodes embedded in nanocapillary array membranes.

Electroosmotic flow (EOF) is used to enhance the delivery of Fe(CN)(6)(4-)/Fe(CN)(6)(3-) to an annular nanoband electrode embedded in a nanocapillary array membrane, as a route to high efficiency electrochemical conversions. Multilayer Au/polymer/Au/polymer membranes are perforated with 10(2)-10(3) cylindrical nanochannels by focused ion beam (FIB) milling and subsequently sandwiched between two axially separated microchannels, producing a structure in which transport and electron transfer reactions are tightly coupled. The middle Au layer, which contacts the fluid only at the center of each nanochannel, serves as a working electrode to form an array of embedded annular nanoband electrodes (EANEs), at which sufficient overpotential drives highly efficient electrochemical processes. Simultaneously, the electric field established between the EANE and the QRE (>10(3) V cm(-1)) drives electro-osmotic flow (EOF) in the nanochannels, improving reagent delivery rate. EOF is found to enhance the steady-state current by >10× over a comparable structure without convective transport. Similarly, the conversion efficiency is improved by approximately 10-fold compared to a comparable microfluidic structure. Experimental data agree with finite element simulations, further illustrating the unique electrochemical and transport behavior of these nanoscale embedded electrode arrays. Optimizing the present structure may be useful for combinatorial processing of on-chip sample delivery with electrochemical conversion; a proof of concept experiment, involving the generation of dissolved hydrogen in situ via electrolysis, is described.

Plasmonic response of electrified metal-liquid interfaces during faradaic and non-faradaic reactions by enhanced optical transmission.

Thin Au films, patterned by focused ion beam (FIB) milling to contain an array of subwavelength nanopores, exhibit enhanced optical transmission (EOT) via front-back resonance coupling. The films also serve as working electrodes capable of controlling the local potential, allowing electrochemical processes to be monitored using wavevector-resolved spectral mapping. The precise value of the surface plasmon resonance (SPR) wavevector can be extracted from the enhanced optical transmission signal and correlated with several distinct classes of electrochemical processes: double layer reorganization, faradaic adsorption/desorption, heterogeneous electron transfer, and anion adsorption. Specifically, the protonation/deprotonation reaction of an adsorbed monolayer of 4-mercaptobenzoic acid, the adsorption/desorption reaction of dodecanethiol to Au, the solution-phase reaction of ferri-ferrocyanide, and sulfate adsorption/desorption are investigated. A simple model is presented that encompasses both the EOT signal and electrochemical processes and produces semi-quantitative agreement with the SPR spectral wavevector mapping observed experimentally.

Electrokinetic control of fluid transport in gold-coated nanocapillary array membranes in hybrid nanofluidic-microfluidic devices.

The introduction of metallic elements into microfluidic devices that support electrokinetic transport creates several fundamental issues relative to the high conductivity of the metal, which can act as a current shunt, causing profound effects on the transport process. Here we examine the use of Au-coated nanocapillary array membranes (Au NCAMs) as electrically addressable fluid control elements in multi-layer microfluidic architectures. Three alternative methods for fluid injection across Au NCAMs are presented: electrokinetic injection across NCAMs with Au coated on one side (asymmetric NCAM), electrokinetic injection across NCAMs with an embedded Au layer (symmetric NCAM), and field-free electroosmotic flow (EOF) pumping across either type of Au NCAM. Injection efficiency across asymmetric NCAMs depends on the orientation of the asymmetric membrane relative to the driving potential. Efficient injections are enabled when the Au coating is on the receiving side of the membrane, however, some distortion of the injected volume element is observed, especially with large injection potentials. These results for asymmetric membranes agree qualitatively with two-dimensional numerical simulations of injections across a single slit pore, which suggest that the direction-selective transport behavior is related to electrophoretic transport of the anionic fluorescein probe. Reproducible, high quality injections are also achieved in symmetric Au NCAMs having an embedded gold nanoband region within the nanopores. Nanoband Au NCAMs are excellent candidates for a range of applications, including high efficiency electrochemical sensing, electrochemically catalyzed conversion or pretreatment and label free sensing utilizing extraordinary optical transmission. EOF pumping could be an alternative to electrokinetic injections in some applications, however, this approach is only useful for relatively large pore sizes (>400 nm) and presents considerably worse sample spreading via Taylor dispersion.

Wavevector-resolved monochromatic spectral imaging of extraordinary optical transmission through subwavelength aperture arrays.

A technique for wavevector-resolved spectroscopic imaging of extraordinary optical transmission (EOT) is developed and tested. The approach allows a large fraction of the first Brillouin zone to be mapped at a single wavelength, thereby greatly increasing the efficiency of sensitivity mapping experiments. An axially opposed, matched pair of microscope objectives constitutes the core of the apparatus. The condensing lens defines a broad range of wavevectors incident upon the sample, while the second objective with a higher numerical aperture collects all of the light transmitted through the sample. In this way, information related to transmission efficiency over a broad range of in-plane wavevectors is preserved at different spatial coordinates in the final image. A periodically structured gold film, consisting of a square array of cylindrical pores, measuring 90 x 90 pores, 100 nm in diameter, with a lattice constant of 1.1 microm, was chosen for detailed study. Direct imaging of the EOT efficiency simultaneously across the range 0 < kx < 0.001 nm(-1), or 20% of the first Brillouin zone, was accomplished, although this was not the limit of the instrument. The experiment was repeated across 21 values of the wavelength and 7 values of the refractive index, to construct a 4-dimensional data set of transmission efficiency with respect to lambda, kx, and n. This technique is compatible with any of the subwavelength aperture array-based chemical sensing methods reported in the literature, however it offers faster transduction of the full spectrum of plasmonic resonant shifts.

Enzymatic activity of surface-immobilized horseradish peroxidase confined to micrometer- to nanometer-scale structures in nanocapillary array membranes.

Horseradish peroxidase (HRP) was immobilized on the planar surfaces and inside the cylindrical nanopores of nanocapillary array membranes (NCAMs) to study how the enzyme-catalyzed oxidation of a fluorigenic substrate, Amplex Red (AR), to fluorescent resorufin by hydrogen peroxide is influenced by confinement. Because AR was also found to be converted to resorufin photolytically at high laser fluences, a modified laser-induced fluorescence protocol was developed to characterize the enzyme-catalyzed reaction in the absence of interference from the photolytic reaction. Surface-immobilized HRP was studied in two environments: bound to the surface of a microfluidic channel, and bound to the interior of cylindrical nanopores in NCAMs connecting crossed microfluidic channels. HRP was immobilized through reaction of solvent-accessible primary amines with the epoxy group of the methyl methacrylate-glycidyl methacrylate copolymer synthesized in either planar or annular geometries to construct the test structures for enzymatic activity. HRP immobilized on planar surfaces shows high activity (approximately 10 microM min(-1)) meaning that the copolymer membrane exhibits good potential for immobilizing the enzyme, especially since active structures are obtained in a one-step reaction. HRP was also immobilized inside nanopores via physisorption. Enzymatic reactions inside the nanopores were characterized and compared to finite element simulations of a modified Eley-Rideal mechanism to bracket the value of the overall rate constant for the confined enzyme. Reaction velocities were estimated to be approximately 10-fold higher in the nanopores than for the same enzyme bound to a planar microfluidic surface.

Single-molecule enzyme dynamics of monomeric sarcosine oxidase in a gold-based zero-mode waveguide.

The localization of optical fields is a powerful method of reducing spectroscopic background signals, enabling studies of single fluorescent molecules. Zero-mode waveguides (ZMWs) strongly confine optical fields to zeptoliter (zL, 10(-21) L) volumes and can be coupled with fluorescence microscopy to study the dynamics of single enzyme molecules due to their excellent optical confinement, precise positioning, and massive parallelism. The experiments described here exploit arrays of gold-based (Au-based) nanopores derivatized with single copies of the redox enzyme monomeric sarcosine oxidase (MSOX). MSOX contains a covalently bound flavin adenine dinucleotide (FAD) cofactor, which is highly fluorescent in the oxidized state and dark in the reduced state, thus producing a characteristic on-off fluorescence signal synchronous with transitions between oxidation states. Although aluminum (Al) is the common choice for the metallic overlayer in ZMW construction, Au is used here to access its unique surface-binding chemistry. In particular, the signal-to-noise ratio is improved for Au-based ZMWs by selective Au passivation. For MSOX reactions involving both the nominal substrate (sarcosine) and an analogous substrate (proline), statistical analysis of single-molecule temporal trajectories reveals the static heterogeneity of single-enzyme reaction rates, but no dynamic disorder. In addition, the single-molecule data confirm the independence of reduction and oxidation reactions. These structures open the way for systematic studies of the effect of molecular crowding on enzyme dynamics.

Electrolysis in nanochannels for in situ reagent generation in confined geometries.

In situ generation of reactive species within confined geometries, such as nanopores or nanochannels is of significant interest in overcoming mass transport limitations in chemical reactivity. Solvent electrolysis is a simple process that can readily be coupled to nanochannels for the electrochemical generation of reactive species, such as H(2). Here the production of hydrogen-rich liquid volumes within nanofluidic structures, without bubble nucleation or nanochannel occlusion, is explored both experimentally and by modeling. Devices comprised of multiple horizontal nanochannels intersecting planar working and quasi-reference electrodes were constructed and used to study the effects of confinement and reduced working volume on the electrochemical reduction of H(2)O to H(2) and OH(-). H(2) production in the nanochannel-embedded electrode reactor output was monitored by fluorescence emission of fluorescein, which exhibits a pH-dependent emission intensity. Initially, the fluorescein solution was buffered to pH 6.0 prior to stepping the potential cathodic of E(0)' for the generation of OH(-) and H(2). Because the electrochemical products are obtained in a 2:1 stoichiometry, local measurements of pH during and after the cathodic potential steps can be converted into H(2) production rates. Independent experimental estimates of the local H(2) concentration were then obtained from the spatiotemporal fluorescence behavior and current measurements, and these were compared with finite element simulations accounting for electrolysis and subsequent convection and diffusion within the confined geometry. Local dissolved H(2) concentrations were correlated to partial pressures through Henry's Law and values as large as 8.3 atm were obtained at the most negative potential steps. The downstream availability of electrolytically produced H(2) in nanochannels is evaluated in terms of its possible use as a downstream reducing reagent. The results obtained here indicate that H(2) can easily reach saturation concentrations at modest overpotentials.